Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups

Definitions

• the present invention relates to a fluorine-containing composition and a process for preparing the same.
• the fluorine-containing composition comprises a fluorine-containing compound or polymer.
• compositions containing fluorine have been used as a releasing agent, an additive for a foam fire extinguisher, a foam stabilizer for expanded materials, a mixing assistant for resins, an antistatic agent, etc., as described, e.g., in Japanese Patent Publication No. 11325/82.
• the performance thereof is not fully satisfactory for practical use.
• such conventional fluorine-containing compositions are water-insoluble, and thus they cannot be used for the purpose of reducing the surface tension of water.
• an object of the present invention is to provide a fluorine-containing composition which is advantageously used as a surface active agent, etc.
• Another object of the present invention is to provide a process for preparing a fluorine-containing composition which is advantageously used as a surface active agent, etc.
• the present invention relates to a fluorine-containing composition represented by formula (I) ##STR4## wherein X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms; R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms; n represents an integer of from 2 to 3; p represents an integer of from 1 to 100; and Y represents a group represented by formula (II) or formula (III) ##STR5## wherein R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms; n represents an integer of from 2 to 3; and Z represents an iodine atom, a sulfonate group, or a sulfate group, ##STR4## wherein X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms; R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms;
• the present invention provides a process for preparing a fluorine-containing composition represented by formula (IV) ##STR7## wherein X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms; R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms; n represents an integer of from 2 to 3; p represents an integer of from 1 to 100; and Y 1 represents a group represented by formula (II) or formula (V) ##STR8## wherein R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms; n represents an integer of from 2 to 3; and Z represents an iodine atom, a sulfonate group, or a sulfate group, ##STR9## wherein R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms; n represents an integer of from 2 to 3; and Z 3 represents an iodine atom,
• X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms
• Z 2 represents a sulfonate group, a sulfate group, an iodine atom, a bromine atom, or a chlorine atom
• X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms
• R represents a hydrogen atom or an aliphatic group having from 1 to 3 carbon atoms
• n represents an integer of from 2 to 3
• p represents an integer of from 1 to 100
• X represents a group containing a polyfluoroaliphatic group having from 3 to 26 carbon atoms
• Z 4 represents an iodine atom, a sulfonate group, or a sulfate group
• ring opening polymerizing occurs when p of formulae (IV) and (VIII), which represent the fluorine-containing compositions obtained by the respective processes, is at least 2.
• the fluorine-containing composition according to the present invention in which Y in formula (I) represents a group represented by formula (II) or formula (III) while Z 1 in formula (III) represents an iodine atom, a bromine atom, a chlorine atom, can be obtained by step (1) only.
• step (2) when the composition obtained in step (1) has the propagating end group represented by formula (II), such composition can be converted into the fluorine-containing composition of the present invention in which Y in formula (I) is represented by formula (III) wherein Z 1 is a hydroxyl group by reacting with an aqueous alkaline solution.
• the number of the carbon atoms contained in the group represented by X is preferably from 5 to 15 in view of the performance as surface active agent of the composition obtained.
• the number of the fluorine atoms is preferably the same number as the carbon atoms contained therein or more, and more preferably 1.5 times the number of the carbon atoms contained therein or more.
• n is not limited, but if n is from 2 to 3, the raw material can be obtained easily.
• the unit or number of the repeating units p can be controlled by adjusting the ratio of the polymerization initiator to the cyclic iminoether upon reaction, or wherein p is at least 2, upon polymerization reaction.
• the fluorine-containing composition is a fluorine-containing polymer when p is at least 2, and when p is 2 or 3, the fluorine-containing polymer is an oligomer.
• the fluorine-containing composition includes fluorine-containing polymers in which p is an average number of repeating units of 2 to about 13.
• the fluorine-containing composition is a fluorine-containing compound when p is 1.
• the fluorine-containing composition of the present invention preferably has a number of the repeating units p of 50 or less.
• any compound having an ionic property e.g., represented by (X) + . (Z 2 ) - , and having no adverse effect on the ring opening of the present invention can be used.
• X + attacks the nitrogen atom of the cyclic iminoether.
• Z 2 is an iodine atom, a sulfonate group, or a sulfate group
• the corresponding onium salt is formed, and (Z 2 ) - becomes the counter ion of the propagating end group (formula (II)).
• Examples of the group represented by X include groups represented by formulae (X-1), (X-2), (X-3), (X-4), or (X-5)
• i represents an integer of from 4 to 22
• j represents an integer of from 1 to 4
• k represents 1 or 2
• R 2 and R 3 which may be the same or different, each represents a hydrogen atom or a methyl group.
• X represents a group represented by formula (X-1) above wherein j represents 2.
• Examples of the sulfonate group represented by Z include a trifluoromethane sulfonate group, a benzene sulfonate group, a p-toluene sulfonate group (tosyl group), etc.
• Examples of the sulfate group represented by Z include an alkyl sulfonate group such as a methyl sulfonate group, an ethyl sulfonate group, etc.
• Z represents a p-toluene sulfonate group (tosyl group).
• the molar ratio of the cyclic iminoether to the polymerization initiator can be freely varied, but preferably is from 0.1/1 to 500/1, and more preferably from 0.5/1 to 50/1.
• the polymerization temperature is preferably from 0 to 200° C., and more preferably from 60° to 120° C.
• an aprotic solvent such as dimethyl formamide, acetonitrile, etc., is preferably used.
• the aqueous alkaline solution preferably has a concentration of from 1 to 20 wt %, and preferably used in large excess based on the amount of the polymer obtained in step (1).
• the reaction temperature in step (2) is preferably from 10° to 50° C.
• a fluorine-containing polymer of the present invention is produced by steps (1) and (2).
• reaction mixture is poured into a mixed solvent of diethyl ether and chloroform (1/1 by volume) to precipitate the thus formed polymer.
• the polymer is collected by decantation, dissolved in chloroform, and reprecipitated from the above mixed solvent, followed by drying under reduced pressure to obtain 1.66 g of yellow waxy polymer (yield: 64%).
• the waxy polymer obtained in the step (1) is added to 20 ml of a sodium hydroxide aqueous solution (5 wt %), and stirred for 30 minutes at 20° C. Then, the components other than the desired polymer are extracted by dichloromethane, and the polymer is dried under reduced pressure to obtain 1.50 g of polymer A' represented by formula (A') (yield: 64%). ##STR15##
• the molecular weight analysis is carried out by using an osmometer (Hitachi, Ltd., Model 117, solvent: chloroform, at 40° C.). The average number of the repeating units is calculated from the molecular weight.
• the NMR analysis is carried out by using an NMR spectrometer (Hitachi, Ltd., Model R-200).
• the IR analysis is carried out by using an infrared absorption spectrometer (Hitachi, Ltd., Model 260-20).
• polymers B', C', and D' are designated polymers B', C', and D', respectively.
• Polymers B' to D' are analyzed in the same manner as in Example 1, and the results obtained are indicated below.
• a fluorine-containing polymer of the present invention is produced by steps (1) and (2).
• reaction mixture is poured into a mixed solvent of diethyl ether and hexane (1/1 by volume) to precipitate the thus formed polymer.
• the polymer is collected by decantation, dissolved in chloroform, and reprecipitated from the above mixed solvent, followed by drying under reduced pressure to obtain 0.26 g of yellow waxy polymer (yield: 23%).
• step (1) The waxy polymer obtained in step (1) is added to 20 ml of a sodium hydroxide aqueous solution (5 wt %), and stirred for 30 minutes at 20° C. Then, the components other than the desired polymer are extracted by dichloromethane, and the polymer is dried under reduced pressure to obtain 0.22 g of the polymer E' represented by formula (E') (yield: 23%).
• E' represented by formula (E')
• a fluorine-containing polymer of the present invention is produced only by step (1).
• a mixture of 1.62 mmol of a polymerization initiator represented by n-C 8 F 17 CH 2 CH 2 I, 32.4 mmol of a cyclic iminoether represented by formula (E), and 10 ml of dimethylformamide is placed in a test tube provided with a magnetic stirrer and a three-way cock. Then the test tube is sealed and heated to 80° C. for 40 hours while stirring.
• a fluorine-containing polymer of the present invention is produced by steps (1) and (2).
• reaction mixture is poured into a mixed solvent of diethyl ether and hexane (1/1 by volume) to precipitate thus formed polymer.
• the polymer is collected by decantation, dissolved in chloroform, and reprecipitated from the above mixed solvent, followed by drying under reduced pressure to obtain a polymer.
• step (1) The polymer obtained in step (1) is added to 20 ml of a sodium hydroxide aqueous solution (5 wt %), and stirred for 30 minutes at 20° C. Then, the components other than the desired polymer are extracted by dichloromethane, and the polymer is dried under reduced pressure to obtain the polymer G' according to the present invention.
• Polymers A', B', C', D', E', E", F” and G' obtained in Examples 1 to 8, respectively, each are dissolved in water to make 0.1 wt % aqueous solutions, and measured for the surface tension of the aqueous solutions by Wilhelmy method at 20° C., by using Kyowa CBVP Surface Tension Meter A1. The results obtained are mentioned in the following Table 1.
• the fluorine-containing polymer according to the present invention can greatly reduce the surface tension of water by a small amount. Therefore, the fluorine-containing composition of the present invention is used advantageously as an additive for a foam fire extinguisher, a mixing assistant for resins, an antistatic agent, a foam stabilizer for expanded materials, a releasing agent, an antisticking agent, etc.
• the fluorine-containing composition of the present invention can be prepared easily.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyethers (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
• Lubricants (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (1)

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Cited By (4)

Citations (8)

Family Cites Families (1)

• 1986
  • 1986-05-07 JP JP61105721A patent/JPS62260830A/ja active Granted
• 1987
  • 1987-05-05 DE DE8787106505T patent/DE3772834D1/de not_active Expired - Lifetime
  • 1987-05-05 EP EP87106505A patent/EP0244828B1/en not_active Expired
• 1988
  • 1988-09-20 US US07/246,748 patent/US4958005A/en not_active Expired - Lifetime

Patent Citations (8)

Non-Patent Citations (1)

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